Di(omega-hydroxyalkyl) cyclopentanes



United States Patent 3,419,622 DI(w-HYDROXYALKYL) CYCLOPENTANES ErichMarcus, Charleston, and Donald L. MacPeek,

South Charleston, W. Va., assignors to Union Carbide Corporation, acorporation of New York No Drawing. Original application Dec. 28, 1962,Ser. No. 247,828, now Patent No. 3,358,008. Divided and this applicationMar. 20, 1967, Ser. No. 624,148

3 Claims. (Cl. 260-617) ABSTRACT OF THE DISCLOSURE This inventionrelates to the production of a member selected from the group consistingof l-hydroxymethyl-Z- hydroxyethylcyclopentane anddi(w-hydroxyalkyl)cyclopentane of the formula:

wherein y and z designate integers of from to 8, at least one of whichis a positive integer, by reacting 1,5-cyclooctadiene with anisoalkylaluminum, optionally growing the resulting polymer withethylene, oxidizing the polymer, and then hydrolyzing the oxygenatedpolymer.

Specification This application is a division of application Ser. No.247,828, entitled Dialiphatic-Substituted Cyclopentanes, filed Dec. 28,1962, now Patent No. 3,358,008.

The present invention is concerned with a novel process for theproduction of dialiphatic-substituted cyclopentanes, including polymericorganoaluminum compounds, utilizing 1,5-cyclooctadiene and anisoalkylaluminum as initial reactants. The invention is also concernedwith certain of the dialiphatic-substituted cyclopentanes, particularlythe polymeric organoaluminum compounds and the higher molecular Weightdienes, monoand diepoxides, and diols hereinbelow described as novel anduseful compositions of matter. In addition, the invention provides forthe production of novel monoaliphatic substituted cyclooctenes,including alkeuyland hydroxyalkyl-substituted cyclooctenes as well asthe corresponding alkenyland epoxyalkyl-substituted epoxycyclooctanes.

In accordance with this invention, 1,5-cyclooctadiene is initiallyreacted with an isoalkylaluminum so as to form a novel polymer composedof recurring l-aluminomethyl- 2-aluminoethylcyclopentane units. Thisreaction can be represented by the partial equation:

R +2al (1112011 i" 3 [8. 6 HDUC H2 0 H231] +2 C Hz: C

3,419,622 Patented Dec. 31, 1968 "ice mer is also composed of terminalaluminocyclooctene units of the formula:

III /R R A1 0111011 and HA1 oHzoE r wherein R is as defined above.Suitable isoalkylaluminums include, by way of illustration,triisobutylaluminum, tri- Z-methylbutylaluminum,tri-2-ethylhexylaluminum, diisobutylaluminum hydride,di-2-methylbutylaluminum hydride, di-Z-ethylhexylaluminum hydride, andthe like. The preferred isoalkylaluminum is triisobutylaluminum.Isoalkylalurninums containing two or three dlitferent isoalky-l radicalscan also be employed as a reactant.

In producing the 1-aluminomethyl-Z-aluminoethylcyclopentane-containingpolymer in accordance with this invention, the proportion of1,5-cyclooctadilene to isoalkylaluminum can vary broadly. Preferably, aproportion of from about 1 to about 5 moles of 1,5-cyclooctadiene permole of isoalkylaluminum is charged, although proportions outside thisrange can also be employed. In addition, when desired, an inert organicsolvent can be incorporated in the reaction mixture. Suitable solventsinclude, for instance, heptane, octane, decane, benzene, toluene,Xylene, decalin and the like. Excess l,5 -cyclooctadiene also serves asa solvent.

The reaction temperature can vary broadly in the range of from about C.to about 180 C., substantially lower temperatures engendering anexcessively slow rate of reaction, while at higher temperatures,undesirable side reactions may occur. Preferably, a reaction temperatureof from about C. to about C. is employed. At such temperatures, thereaction is generally carried out for a period of from about 1 to about10 hours. However, longer or shorter reaction periods sufiicient toproduce the desired polymer can also be employed.

It has also been found preferable, during the course of the reaction, toremove the isoolefin formed as a byproduct. Concordaut therewith, thereaction can be carried out in an open system under atmosphericpressure, or in a closed system under autogenous pressure providing thesystem is equipped, in the latter instance, with means for venting orremoving the by-product. The removal of by-product isoolefin serves todrive the reaction to completion and minimizes or eliminates sidereactions between the isoolefin and the growing polymer.

The polymer thus obtained is ordinarily liquid at room temperature, andcan be recovered from the reaction mixture, in any convenient manner.For instance, the polymer can be recovered as the residue productobtained upon removal of the more volatile components of the reactionmixture by distillation or evaporation, etc.

In another aspect of this invention, when a polymer containing recurringdi(aluminoalkyl)cyclopentane units of higher molecular weight, i.e.increased aluminoalkyl chain length, is desired, the polymer obtained asdescribed above is subsequently subjected to a growth process byreaction with ethylene in the absence of a catalyst, and

xCHz=OHz [alCH CHzCHzlal wherein y and z designate integers of from O toa positive value, at least one of which must be a positive value as aconsequence of the reaction with ethylene; the sum of y plus z beingequal to x, the number of moles of ethylene added per recurring unit ofthe polymer. Thus, in the growth process ethylene units are insertedbetween aluminum atoms and adjacent carbon atoms. A similar growthprocess will also occur in any minor amounts of other recurring unitspresent in the polymer, as well as in terminal groups. Accordingly, thegrown polymer will contain terminal aluminoalkylcyclooctene units of theformula:

wherein y is a positive value within the meaning hereinabove defined byy. In addition, the grown polymer will contain a minor amount ofrecurring and terminal units which have not reacted with ethylene.

The amount of ethylene reacted should be suflicient to effect the growthof the recurring units of the polymer to the extent desired, asdetermined, for instance, by the subsequent use of the grown polymer.Useful polymers, by way of illustration, are those in which thealuminoalkyl chain length of the recurring units have grown by astatistically varying length of from 2, and preferably from 6, to about32 carbon atoms, i.e. wherein y and z designate integers having a valueof from zero to about 8, at least one of which has a positive value, thesum of which is preferably a value of at least 3. To this end, thepolymer for which growth is desired is reacted with ethylene in aproportion of at least 1.5 moles, and preferably from about 4.5 moles,to about 24 moles of ethylene per atom of aluminum present in thepolymer or per mole of isoalkylaluminum initially reacted to produce thepolymer. In practice, however, an excess over the required amount ofethylene is generally charged. If desired, an inert organic solvent suchas those described in connection with the initial polymer formation canalso be incorporated in the reaction mixture.

The reaction temperature for the growth process can vary broadly in therange of from about 80 C. to about 190 C., substantially lowertemperatures engendering an excessively slow rate of reaction, while athigher temperatures, undesirable side reactions may occur. Preferably areaction temperature of from about 85 C. to about 120 C. is employed,particularly in connection with a batch operation. At such temperatures,the reaction is generally carried out for a period of from about 5 toabout 50 hours. However, longer or shorter reaction periods consistentwith the production of the grown polymer can also be employed. Thus, forinstance, the reaction can also be carried out continuously in a tubularreactor at a temperature preferably of from about 120 C. to about 190 C.for very short contact periods. The amount of ethylene entering thepolymer can be controlled in part by the control of temperature,reaction period, etc., and is readily determinable by one skilled in theart in light of this disclosure.

After the desired amount of ethylene has been incorporated in thepolymer as determined for instance, by the moles of ethylene consumed,the system is vented so as to remove any excess ethylene. The grownpolymer thus obtained, like its polymeric precursor, is ordinarilyliquid at room temperature, and can be recovered from the reactionmixture in any convenient manner, as for instance, by the techniquesdescribed above in connection with the recovery of the ungrown polymer,

In still another aspect of the invention, the polymeric productshereinabove described are subjected to a displacement process bysubsequent reaction with ethylene in the presence of a catalyst, andpreferably under pressure, to form a useful class of dienes, viz.di(w-alkenyl) cyclopentanes. In one embodiment of this aspect of theinvention, when using an ungrown polymer, i.e. the polymer obtained inaccordance with Equation I, the catalyzed reaction with ethylene can berepresented by the partial equation:

VII

Catalyst wherein y and z are as defined above. Alternatively, when thegrown polymer is such that y is zero, the catalyzed reaction withethylene can be represented by the partial equation:

VIII

wherein the double bond of the methylene radical attached directly tothe cyclopentane nucleus is attached to a single carbon atom thereof,and z is a positive value within the meaning hereinabove defined by z. Asimilar displacement process also occurs in any minor amounts of otherrecurring units present in the polymer as well as in terminal units.Thus, when the polymer undergoing reaction is an ungrown polymer,cyclooctadiene is simultaneously derived from the terminalaluminocyclooctene units of the polymer. Similarly, when the polymerundergoing reaction is a grown polymer, the terminalaluminoalkylcyclooctene units are converted to w-alkenylcyclooctenesrepresented by the formula:

wherein y is as defined above.

In the displacement process, the polymer is reacted with ethylene in aproportion of at least 3 moles of ethylene per atom of aluminum presentin the polymer. In practice, however, an excess over the required amountof ethylene is generally charged. If desired, an inert Catalyst organicsolvent such as those described above in connection with the initialpolymer formation can also be in corporated in the reaction mixture. Inaddition, the presence of a small amount of an acetylenic compound, suchas phenylacetylene, has been found to minimize the migration of doublebonds in the diene product.

Suitable catalysts for use in the displacement process include nickel,cobalt, and platinum. Such metals can be incorporated in the reactionmixture in elemental form, or preferably, as an inorganic or organicsalt, such as nickel chloride, platinum chloride, cobalt chloride,nickel acetylacetonate, platinum acetylacetonate, cobaltacetylacetonate, and the like. The use of such salts ordinarilyengenders a better dispersion of the metal in the reaction mixture. Thecatalyst is generally employed in a concentration of from about 0.0001to about 1 percent by weight of metal based upon the weight of thepolymer undergoing reaction, although higher or lower catalytic amountscan also be used. Preferably, the catalyst is employed in aconcentration of from about 0.005 to about 0.1 percent by weight basedin like manner.

The reaction temperature for the displacement process can vary broadlyin the range of from about C. to about 120 C., particularly inconnection With a batch operation. Here again substantially lowertemperatures engender an excessively slow reaction rate, while at highertemperatures, in the presence of the catalyst, undesirable sidereactions may occur. The preferred reaction temperature is from about 40C. to about 70 C. At such temperatures the reaction is generally carriedout for a period of from about 1 to about 24 hours. However, longer orshorter reaction periods consistent with diene formation can also beemployed.

The displacement process can also be conducted omitting the use of acatalyst at substantially higher reaction temperatures of from about 250C. to about 350 C. or slightly higher, and preferably from about 280 C.to about 320 C. At such higher temperatures, the reaction is bestcarried out continuously in a tubular reactor for short contact periods.

The diene product thus obtained is ordinarily liquid at room temperatureand can be recovered from the reaction mixture in any convenient manner.For instance. the product can be recovered as the residue obtained uponremoval of the more volatile components of the reaction mixture bydistillation. Alternatively, the reaction mixture can be hydrolyzed toassist the removal of alkylaluminum formed as a by-product. Hydrolysiscan be effected by reaction with water, aqueous alcohol, and/ or diluteacid. Upon hydrolysis, aluminum hydroxide is formed. The diene productcan then be recovered by distillation of the organic phase of thereaction mixture. The removal of by-product alkylaluminum in this mannerprevents the reversal of the displacement process which might otherwiseoccur upon distillation of the diene product.

Due to the nature of the polymer employed as precursor, the dieneproduct may comprise an isomeric mixture of1,2-di(w-al-kenyl)cyclopentanes of statistically varying molecularWeight (alkenyl chain length) in both trans and cis forms, the lattergenerally predominating in the product. In addition, cyclooctadiene andw-alkenylcyclooctenes of statistically varying molecular weight are alsoproduced. Such mixture can be resolved into components of narrow carboncontent ranges by fractional distillation and the products analyzed bygas chromatography.

As typical of the di(w-alkenyl)cyclopentanes produced in accordance withthis invention, there can be mentioned:.

1-methylene2-vinylcyclopentane,

1-methylene-2- 3-butenyl cyclopentane,1-methylene-2-(5-hexenyl)cyclopentane,1-methylene-2-(7-octenyl)cyclopentane, 1-rnethy1ene-2- 9-decenylcyclopentane,

1- 2-propenyl)-2- S-butenyl cyclopentane, 1- 2-propeny1 -2- (7 -octenylcyclopentane, 1- (4-pentenyl) -2- S-hexenyl cyclopentane, 1-(4-pentenyl) -2 9-decenyl) cyclopentane, 1- (4-pentenyl -2-(17-octadecenyl cyclopentane,

and the like. Similarly, as typical of the w-alkenylcyclo octenesproduced in accordance with this invention, there can be mentioned5-vinylcyclooctene, 5-(3-butenyl)cyclooctene, S-(S-hexenyl)cyclooctene,5-(7-octenyl)cyclooctene, 5-(1S-hexadecenyl)cyclooctene, and the like.The higher molecular weight di(w-alkenyl)cyclopentenes containing from14 to about 40 carbon atoms and the walkenylcyclooctenes arecontemplated as novel composi tions of matter.

The dienes can subsequently be polymerized in accord ance withconventional processes for the polymerization of olefinicallyunsaturated compounds to produce useful polymers. Thedi(w-alkenyl)cyclopentanes: can also be reacted in accordance withconventional processes for the epoxidation of olefinically unsaturatedcompounds to produce the vicinal monoand diepoxides represented by theformulas:

the the epoxide product will depend upon the diene employed as aprecursor. For instance, the epoxides represented by formulas X (a) and(b) are derived from the di(w-alkenyl)cyclopentanes obtained inaccordance with Equation VI; the epoxides represented above by FormulasXI (a) to (c) are derived from the di(w-alkenyl)- cyclopentanes obtainedin accordance with Equation VII; and the epoxides represented byFormulas XII (a) and (b) are derived from the di(w-alkenyl)cyclopentanesobtained in accordance with Equation VIII. In similar manner, thew-alkenylcyclooctenes produced in accordance with this invention areepoxidized to yield the vicinal monoand di-epoxides represented by theformula:

wherein y is as defined above, while vicinal epoxycyclooctenes anddiepoxycyclooctanes are derived from the cyclooctadiene.

The formation of a mono-or diepoxide will depend for the most part uponthe amount of epoxidizing agent employed, and is readily determinable byone skilled in the art in light of this disclosure. It is to be notedthat the reaction of the di(w-alkenyl)cyclopentanes obtained inaccordance with Equations VI and VIII with an amount of epoxidizingagent suflicient to produce a monoepoxide will generally result in theepoxidation of the bare methylene radical attached to the cyclopentanenucleus rather than the higher w-alkenyl radical. Under similarconditions, the epoxidation of the w-alkenylcyclooctenes selectivelyepoxidizes the unsaturation in the cyclooctene nucleus. On the otherhand, the reaction of the di(w-.alkenylcyclopentanes obtained inaccordance with Equation VII with an amount of epoxidizing agentsufficient to produce a monoepoxide may result in the production of anisomeric mixture of the epoxides represented by Formula XI (a) and (b).Mixtures of monoand diepoxides may also be produced dpeending, forinstance, upon the amount of epoxidizing agent employed.

The epoxidation of the dienes can be carried out by reaction Withperacetic acid or other conventional epoxidizing agent, in a suitablesolvent such as ethylacetate, if desired, and at a temperature which canvary broadly in the range of from about -25 C. to about 150 C.Preferably, reaction temperatures of from about 10 C. to about 90 C. areemployed. At such temperatures, a reaction period of from about 1 toabout 10 hours is usually suflicient for a complete reaction. However,longer or shorter reaction periods consistent with epoxide formation canalso be employed.

The epoxide product can then be recovered from the reaction mixture inany convenient manner. For instance, the epoxide product can berecovered as the residue obtained upon removal of the more volatilecomponents of the reaction mixture by distillation or evaporation, andresolved, if desired, by further distilltaion when more than one epoxideis produced.

As typicals of the epoxides produced in accordance with this invention,there can be mentioned:

1-methyleneoxy-2-( 1,2-epoxyethyl) cyclopentane 1-methyleneoxy-2-3-butenyl) cyclopentane l-methyleneoxy-Z- 5 ,6-epoxyhexyl cyclopentane1-methyleneoxy-2- 7-octenyl cyclopentane1-methyleneoxy-2-(9,10-epoxydecyl) cyclopentane1-(2,3-epoxypropyl)-2-(1,2-epoxyethyl)cyclopentane 1- (2-propenyl -2-3,4-epoxybutyl) cyclopentane 1- (4,5 -epoxypentyl -2- 5 ,6-epoxyhexylcyclopentane 1- 4-penteny1) -2- (7 ,8-epoxyoctyl cyclopentane 1-2,3-epoxypropyl) -2- 3-butenyl) cyclopentane 1- 2,3-epoxypropyl -2-(7-octenyl cyclopentane 1- (2,3-epoxypropyl) -2- (9, 1 O-epoxydecylcyclopentane 1- (4,5 -epoxypropyl -2- 17, 1 8-epoxyoctadecyl)cyclopentane 1,2,5 ,6-diepoxycyclooctane S-vinyl-1,2-epoxycyclooctane5-(1,2-epoxyethyl)-1,2-epoxycyclooctane 5-(3-butenyl)-1,2-epoxycyclooctane 8 5- 3,4-epoxybutyl l ,2-epoxycyclooctane 5- 7,S-epoxyoctyl -1 ,Z-epoxycyclooctane5-(l6,17-epoxyhexadecyl)-1,2-epoxycyclooctane and the like. The highermolecular weight epoxides of Formulas XI and XII containing from 14 toabout 40 carbon atoms, and the epoxides of Formula XIII are contemplatedas novel compositions of matter.

The epoxides produced in accordance with this invention can behomopolyrnerized or reacted with organic hardeners such aspolycarboxylic acids or anhydrides, polyamines, or polyols to producecurable resins having a wide variety of uses, particularly as moldedarticles. The resins thus obtained from the novel epoxides of thisinvention, particularly the diepoxides, and especially those of FormulasXI and XII may be characterized by enhanced impact strength and thermalshock resistance. The novel diepoxides of this invention can also beemployed as plasticizers for vinyl resins. The novel monoepoxides ofthis invention, on the other hand, can be copolymerized withconventional vinyl monomers to produce resins having enhanced heat and/or light stability.

In a further aspect of this invention, the polymers obtained inaccordance with Equations I and IV are converted to a useful class ofdiols, viz. the di(w-hydroalkyl)- cyclopentanes represented by theformula:

XIV

wherein y and 2 independently designate integers of from 0 to 8. Thespecific structure of the diols will depend upon the polymer employed asa precursor. Thus, the diols represented by Formula XIV wherein y and z"each designate zero are derived from the polymer obtained in accordancewith Equation 1; while the diols represented by Formula XIV wherein yand/or 2 designate a positive integer are derived from the grown polymerobtained in accordance with Equation IV, with y" and z" being equal to yand z respectively. At the same time, the olefinically unsaturatedmonohydroxy compounds represented by the formula:

wherein y" is as defined above, are derived from terminal units of thepolymer.

The conversion of the polymer to monoand diols can be carried out bycontacting the polymer at a temperature maintained in the range of fromabout 0 C. to about C., and preferably from about 30 C. to about 60 C.,with oxygen so as to insert an oxygen atom between each aluminum atom ofthe polymer and the adjacent carbon atom. Such contact can be elfected,for instance, by passing dry air or a nitrogen-oxygen mixture into areaction mixture containing the polymer. Since the reaction isexothermic, it is desirable in some instances to use a low concentrationof oxygen at the beginning of the reaction and thereafter increase theoxygen concentration in the reactant gas stream as the rate of reactiondecreases. Near the end of the reaction, pure oxygen can be used toinsure completion. If desired, an inert organic solvent such as thosedescribed above in connection with the initial polymer formation canalso be incorporated in the reaction mixture.

After the oxygenation step, water or dilute acid is added to thereaction mixture to convert the oxygenated polymer to the monoand diols.Water is preferred, as it readily hydrolyzes the polymer, forming themonoand diols and aluminum hydroxide as a by-product. Alternatively, theoxygenated polymer can be hydrolyzed by reaction with aqueous alcohol.

The monoand diols thus obtained can be recovered from the reactionmixture in any convenient manner, as for instance, by distillation ofthe organic phase of the reaction mixture, etc. Moreover, due to thenature of the polymers employed as precursors, the product may comprisean isomeric mixture of 1,2-di(w-hydroxyalkyl)cyclopentanes ofstatistically varying molecular weight (hydroxyalkyl chain length) inboth trans and cis forms, the latter generally predominating in theproduct. In addition, hydroxycyclooctene and w-hydroxyalkylcyclooctenesof statistically varying molecular weight are also produced. Suchmixture can be resolved into components of narrow carbon content rangesby fractional distillation and the products analyzed by gaschromatography.

As typical of the di(w -hydroxyalkyl)cyclopentanes produced inaccordance with this invention, there can be mentioned:

1 -hydroxymethyl-2- Z-hydroxyethyl cyclopentane l-hydroxymethyl-Z-4-hydroxybutyl) cyclopentane l-hydroxymethyl- 2- 6-hydroxyhexylcyclopentane 1hydroxymethyl-2- S-hydroxyoctyl cyclopentane1-hydroxymethyl-2-( -hydroxydecyl) cyclopentane 1- 3-hydroxypropyl -2-Z-hydroxyethyl cyclopentane 1- 3-hydroxypropyl) -2- (4-hydroxybutyl)cyclopentane 1- S-hydroxypentyl) -2- 6-hydroxyhexyl) cyclopentane 1-S-hydroxypentyl 2- 8-hydroxyoctyl cyclopentane 1( 3-hydroxypropyl) -2-10-hydroxydecyl cyclopentane and the like. Similarly, as typical of thew-hydroxyalkyl cyclooctenes produced in accordance with this invention,there can be mentioned: 5-(Z-hydroxyethyl)cyclooctene,5-(4-hydroxybutyl) cyclooctene, 5- o-hydroxyhexyl cyclooctene, 5 (8hydroxyoctyl)cyclooctene, 5-(15-hydroxyhexadecyl)cyclooctene, and thelike. The higher molecular Weight di(w-hydroxyalkyl)cyclopentanescontaining from 14 to about 40 carbon atoms and the olefinicallyunsaturated monohydroxyalkyl compounds of Formula XV are contemplated asnovel compositions of matter.

The diols produced in accordance with this invention can be employed asorganic hardeners by reaction with diepoxides, such as3,4-epoxy-6-methylcyclohexylmethyl, 3,4 epoxy6-methylcyclohexanecarboxylate, in conventional manner to producecurable resins having a wide variety of uses, particularly as moldedarticles. The resins thus produced from the novel diols of thisinvention may be characterized by enhanced impact strength and thermalshock resistance. The olefinically unsaturatedmonohydroxyalkyl compoundsof Formula XV, on the other hand, can be employed as cross-linkingagents for vinyl resins.

The polymers obtained in accordance with Equations I and IV can also behydrolyzed by reaction with aqueous alcohol and/ or dilute acid to formthe dialkylcyclopentanes represented by the formula:

and the 'alkylcyclooctenes represented by the formula:

XVII

wherein y" and z are as defined above.

The products thus obtained can be recovered from the reaction mixture inany convenient manner, as for instance, by distillation of the organicphase of the reaction mixture. Moreover, due to the nature of thepolymers employed as precursors, the hydrolyzed product may comprise anisomeric mixture of 1,2-dialkylcyclopentanes of statistically varyingmolecular weight (alkyl chain length) in both trans and cis forms, thelatter generally predominating in the product. In addition, cycloocteneand alkylcyclooctenes of statistically varying molecular weight are alsoproduced. Such mixture can be resolved into components of narrow carboncontent ranges by fractional distillation and the products analyzed bygas chromatography.

The dialkylcyclopentanes can also be obtained by the reaction withhydrogen of the di(w-alkenyl)cyclopentanes of Formulas VI to VIII inaccordance with conventional processes for the hydrogenation ofolefinically unsaturated compounds, while alkylcyclooctanes aresimilarly obtained from the w-alkenylcyclooctenes of Formula IX.

The invention, in its various aspects, can be illustrated further by thefollowing examples.

Example I In a one-liter flask equipped with a stirrer, thermometer,condenser, inlet tube and attachment to a Dry Ice trap, 132 grams oftriisobutylaluminum were added with stirring to 216 grams of1,5-cyclooctadiene, over a period of about three hours, at a temperaturemaintained in the range of from 122 C. to 149 C. Heating and stirringwere then continued at a temperature of about 145 C. for an additionalperiod of about one hour. During course of the ensuing reaction, 106grams of isobutylene, formed as a byproduct, were removed. Thereafter,52 grams of unreacted cyclooctadiene were recovered by distillationwithout rectification at a temperature of 55 C. under reduced pressure.A polymeric product composed of recurringl-aluminOmethyl-Zaluminoethylcyclopentane units was formed. The polymerwas hydrolyzed by reaction with 300 milliliters of ethanol at atemperature of about 45 C. Hydrolysis was subsequently continued byreaction with dilute hydrochloric acid at the same temperature. Atwophase reaction mixture comprising an upper organic layer and a loweraqueous layer was formed. The organic layer was separated, combined witha petroleum ether (B.P. 3537 C.) extract of the aqueous layer washedfirst with water, then with dilute sodium hydroxide, and thereafteragain with water, dried over calcium chloride, and fractionallydistilled. The fractions were analyzed by gas chromatography. There werethus obtained as products, 26.5 grams oftrans-1-ethyl-2-methylcyclopentane, 41.3 grams ofcis-1-ethyl-Z-methylcyclopentane, and 16.4 grams of cyclooctene. Inaddition, minor amounts of C hydrocarbons and an isomeric mixture ofcyclooctadienes were also recovered.

Example II In a manner similar to that described above in Example I, 264grams of triisobutylaluminum were treated with 432 grams of1,5-cyclo0ctadiene to produce 339 grams of a polymer composed ofrecurring 1-aluminomethyl-2- aluminoethylcyclopentane units. A mixtureof 320 grams of this polymer, 500 ml. of benzene, and 0.15 gram ofnickel acetylacetonate was charged to a stainless steel bom'b under anitrogen atmosphere. Thereafter, 351 grams of ethylene were added to themixture, and the bomb was closed and heated, accompanied by rocking, toa temperature of 74 C. within a period of 15 minutes. The pressurewithin the bomb at this point was 1080 p.s.i. Heating was continued,accompanied by rocking, at a temperature maintained in the range of from69 C. to 74 C. for a period of 17 hours, whereupon the pressure withinthe bomb had dropped to 680 p.s.i. at 70 C. The bomb was vented at roomtemperature and its contents transferred under a nitrogen atmosphere toa distillation flask. Benzene and other low-boiling material wereremoved by distilaltion without rectification by lowering the pressuregradually to 10 mm. of Hg at 40 C. The distillate was then fractionalydistilled and the fractions analyzed by gas chromatography. In thismanner, about 28 grams of a predominantly l-methylene 2vinylcopentane-containing fraction were recovered at 121 C./ atmosphericpressure to C./20O mm. of Hg. Another predominantly 1-methylene 2vinylcyclopenta-ne-containing fraction (B.P. 122-124 C.) had thefollowing physical properties: n 1.4572, 1 20, 0.814.

Analysis.calculated for C H C, 88.82; H, 11.18; M.W., 108. Found: C,88.55; H, 11.39; M.W., 108.

Two milliliters of the 1-methlyene-2-vinylcyclopentane product (3.1.122-124 C.) were hydrogenated over platinum oxide in a Parr hydrogenatorat 40 p.s.i. and room temperature for a period of about 1 hour. Thepressure at the end of this period was 37.5 p.s.i. There were thusobtained as products trans-and cis-l-methyl-Z-ethylcyclopentanes in anessentially quantitative yield as indicative by gas chromatography.

The l-methylene-2-vinylcyclopentane product is subsequently converted to1-methyleneoxy-2-(1,2-epoxyethyl)cyclopentane by admixing the diene, inethylacetate, with an excess over two moles of peracetic acid per moleof diene, and heating the resulting mixture at a temperature of about 60C. for several hours.

Example III In a manner similar to that described above in Example I,triisobutylaluminum is reacted with 1,5-cyclooctadiene to produce apolymer composed of recurring laluminomethyl-Z-aluminoethylcyclopentaneunits. A mixture of this polymer and benzene are charged to a stainlesssteel bomb under a nitrogen atmosphere. Thereafter, an amount ofethylene approximately equal to twice the weight of the polymer is addedto the mixture, and the bomb is closed and heated, accompanied byrocking, at a temperature of about 85 C. for a period of about one day.An ethylenically grown polymer composed of a proportion of recurringdi(aluminoalkyl)cyclopentane units substantially equal to the proportionof l-aluminomethyl-2-aluminoethylcyclopentane units in the polymericprecursor is formed. The grown polymer is hydrolyzed by reaction withethanol and dilute hydrochloric acid. A two-phase reaction mixturecomprising an upper organic layer and a lower aqueous layer is formed.The organic layer is then separated, washed with water, dried overcalcium chloride, and fractionally distilled, the fractions beinganalyzed by gas chromatography. In this manner, there are obtained asproducts l,2,-C C C C C C C and C -dialkyl)cyclopentanes, i.e.cyclopentanes containing two alkyl substituents possessing an aggregatesum of carbon atoms. A minor amount of similarly grown alkylcyclooctenesis also obtained.

Example IV In a manner similar to that described above in Example III,an ethylenically grown polymer composed of recurringdi(aluminoalkyl)cyclopentane units is produced by the initial reactionof triisobutylaluminum with 1,5- cyclooctadiene to form a polymercomposed of recurring 1-aluminomethyl-Z-aluminoethylcyclopentane units,followed by the reaction of the polymer with ethylene in the absence ofcatalyst. Thereafter, an additional amount of ethylene slightly lessthan the previously charged, together with a catalytic amount of nickelacetylacetonate, is added to the bomb containing the polymer and thebomb is closed and reheated, accompanied by rocking, at a temperature ofabout 90 C. for a period of about one day. The product is hydrolyzed byreaction with ethanol and dilute hydrochloric acid. A two-phase reactionmixture comprising an upper organic layer and a lower aqueous layer isformed. The organic layer is then separated, washed with water, driedover calcium chloride and fractionally distilled, the fractions beinganalyzed by gas chromatography. In this manner, there are obtained asProducts 3' 5, 1, 9, 11': 13, 15, and 17 di-w-alkenyl)cyclopentanes,i.e. cyclopentanes containing two w-alkenyl substituents possessing anaggregate sum of 3, 5, 7, 9, l1, 13, 15 and 17 carbon atoms. A minoramount of similarly grown w-alkenylcyclooctenes is also produced. Thedi(w-alkenyl)cyclopentanes and walkenylcyclooctenes are converted to thecorresponding diepoxides by reaction with excess peracetic acid in amanner similar to that described above in Example II.

1 2 Example V An ethylenically grown polymer, dissolved in benzene, isobtained as described above in Example IV. At a temperature of about 60C., dry air is then passed through the reaction mixture, therebyoxygenating the polymer. Upon completion of the ensuing reaction, asevidenced by a cessation in the evolution of heat, water is added to thereaction mixture, accompanied by heating at a temperature of about C. tohydrolyze the polymer. The precipitated aluminum hydroxide is removed byfiltration. The filtrate is thereafter fractionally distilled. In thismanner, there are obtained as products, 1,2-(C C C C C C C and C-di-w-hydroxyalkyl)cyclopentanes, i.e. cyclopentanes containing twow-hydroxyalkyl substituents possessing an aggregate sum of 3, 5, 7, 9,ll, 13, 15 and 17 carbon atoms. A minor amount of hydroxycyclooctene andsimilarly grown w-hYdIOXY- alkylcyclooctenes is also produced.

What is claimed is:

1. The process for the production of di(w-hydroxyalkyl)cyclopentane ofthe formula:

wherein y and z designate integers from 0 to 8, at least one of which isa positive integer, which process comprises the steps of (a) bringing1,5-cyclooctadiene into reactive admixture with an isoalkylaluminum ofthe formula selected from the group R Al CHaOI-I and HA1 CHzCH whereineach R, independently, designates an alkyl radical of from 1 to 4 carbonatoms, at a temperature of from about 80 C. to about C., for a period oftime sufficient to produce a polymer composed of recurring units of theformula:

[al C H2L -/,C H: C Haal] (b) bringing said polymer into reactiveadmixture with at least 1.5 moles of ethylene per aluminum atom of saidpolymer, in the absence of a catalyst, at a temperature of from about 80C. to about C., for a period of time sufiicient to produce anethylenically grown polymer of the formula:

noougornom),Uwmcm) ,omornou wherein y and z designate integers of from 0to 8, at least one of which is a positive integer, which processcomprises the steps of (a) bringing 1,5-cyclooctadiene into reactiveadmixture with an isoalkylaluminum of the formula selected from thegroup wherein each R, independently, designates an alkyl radical of from1 to 4 carbon atoms, at a temperature of from about 120 C. to about 160C., for a period of time suffieient to produce polymer composed ofrecurring units of the formula:

[al (C Hg C H1) :1 C ZED-U C HICHQEI] (b) bringing said polymer intoreactive admixture with at least 1.5 moles of ethylene per aluminum atomof said polymer, in the absence of a catalyst, at a temperature of fromabout 85 C. to about 120 C., for a period of time sufiicient to producean ethylenically grown polymer of the formula:

References Cited UNITED STATES PATENTS 3,136,607 6/1964 DAlelio 260- 4483,035,077 5/1962 Johnson et al. 260448 LEON ZITVER, Primary Examiner. M.W. GLYNN, Assistant Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION aten 3,419 ,622Dated December 31 1";68

Inventor(s) Erich I-Iarcus 9; 511

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 13, lines- 10-15, the formula should read:

- ECH U Signed and Sea-led this twenty-fifth D ay Of November 19 75 [5:Al. I

Arrest:

RU'BH C. M'ASON C. MARSHALL DANN Aries-ling Officer ('mnmissimwrqfPau'nrs anu' Trmlmnurkx

